KR101921019B1 - Compositions comprising 2,3-dichloro-1,1,1-trifluoropropane, 2-chloro-1,1,1-trifluoropropene, 2-chloro-1,1,1,2-tetrafluoropropane or 2,3,3,3-tetrafluoropropene - Google Patents

Abstract

HCFC-243db, HCFO-1233xf, HCFC-244db and / or HFO-1234yf and at least one further compound. 1234yf, the further compounds are HFO-1234ze, HFO-1243zf, HCFC-243db, HCFC-244db, HFC-245cb, HFC-245fa, HCFO-1233xf, HCFO-1233zd, HCFC-253fb, HCFC-234ab , HCFC-243fa, ethylene, HFC-23, CFC-13, HFC-143a, HFC-152a, HFC-236fa, HCO-1130, HCO-1130a, HFO-1336, HCFC-133a, HCFC- , HFO-1141, HCFO-1242zf, HCFO-1223xd, HCFC-233ab, HCFC-226ba, and HFC-227ca. A composition comprising HCFC-243db, HCFO-1233xf, and / or HCFC-244db is useful in the process of making HFO-1234yf. Compositions comprising HFO-1234yf are useful as heat transfer compositions for use in refrigeration, air conditioning and heat pump systems, among others.

Description

Dichloro-1,1,1-trifluoropropane, 2-chloro-1,1,1-trifluoropropene, 2-chloro-1,1,1,2-tetrafluoropropane COMPOUND COMPRISING 2,3-DICHLORO-1,1,1-TRIFLUOROPROPANE, 2-CHLORO-1,1,1-TRIFLUOROPROPENE, 2-CHLORO -1,1,1,2-TETRAFLUOROPROPANE OR 2,3,3,3-TETRAFLUOROPROPENE}

The present invention relates to a heat transfer composition, an aerosol propellant, a foaming agent, a blowing agent, a solvent, a detergent, a carrier fluid, a displacement drying agent, a buffing abrasion agent, a polymerization medium, a polyolefin and a poly To a field of compositions that may be useful as an expansion agent for urethane, a gaseous dielectric, an extinguishing agent, and a fire suppression agent in liquid or gaseous form. In particular, the present invention relates to compositions that may be useful as heat transfer compositions, such as 2,3,3,3-tetrafluoropropene (HFO-1234yf, or 1234yf) 1-trifluoropropane (HCFC-243db or 243db), 2-chloro-1,1,1-trifluoropropene (HCFO-1233xf or 1233xf), or 2-chloro-1,1,1,2-tetra Fluoropropane (HCFC-244bb).

New environmental regulations have required new compositions for use in refrigeration, air conditioning, and heat pump systems. Compounds with a lower global warming potential are of particular interest.

The present inventors have found that certain additional compounds are present in minor amounts in the preparation of new compounds having such a low global warming index, for example 1234yf.

HFO-1234yf, HFO-1243zf, HCFC-243db, HCFC-244db, HFC-245cb, HFC-245fa, HCFO-1233xf, HCFO-1233zd, HCFC-253fb, HCFC- 234ab, HCFC-243fa, ethylene, HFC-23, CFC-13, HFC-143a, HFC-152a, HFO-1243zf, HFC-236fa, HCO-1130, HCO- There is provided a composition comprising at least one additional compound selected from the group consisting of HFC-214fb, HCFC-1131, HFC-1141, HCFO-1242zf, HCFO-1223xd, HCFC-233ab, HCFC-226ba, and HFC-227ca. The composition contains less than about 1% by weight of at least one additional compound.

A composition comprising HCFC-243db, HCFO-1233xf, and / or HCFC-244db is useful in the process of making HFO-1234yf. Thus, a composition comprising 1234yf may contain some HCFC-243db, HCFO-1233xf, and / or HCFC-244db in addition to other compounds.

Therefore, according to the present invention, it is possible to use HCFC-243db and ethylene, HFC-23, CFC-13, HFC-143a, HFC-152a, HFO-1234yf, HFO-1243zf, HFC-236fa, HCO- HFO-1234ze, HFO-1336, HCFC-244bb, HCFC-244db, HFC-245fa, HFC-245cb, HCFC-133a, HCFC-254fb, HCFC-1131, HCFO-1233xf, HCFO- At least one further compound selected from the group consisting of HFC-223fa, HCF-223fb, HCFO-1223xd, HCFC-233ab, HCFC-226ba, and HFC-227ca. The composition may contain greater than about 0 weight percent to about 99 weight percent HCFC-243db.

HCFC-233ab, HFO-1234yf, HFO-1234ze, ethylene, HFC-23, CFC-13, HCFC-1233xd, HCFO-1232xd, HCFO-1232xd, HCFO-1223xd, HCFC- HFC-143a, HFC-152a, HFO-1243zf, HFC-236fa, HCO-1130, HCO-1130a, HFO-1336, HCFC-244bb, HCFC-244db, HFC-245fa, HFC- At least one further compound selected from the group consisting of HFC-224fa, HCFC-1131, HCFO-1242zf, HCFO-1223xd, HCFC-233ab, HCFC-226ba, and HFC-227ca is further provided. The composition may contain from greater than about 0% by weight to about 99% by weight of HCFO-1233xf.

HFO-1234yf, HFC-23, CFC-13, HCFC-243bb, HCFO-1233zd, HCFO-1232xd, HCFO-1223xd, HCFC-253fb, HCFC- HFC-143a, HFC-152a, HFO-1243zf, HFC-236fa, HCO-1130, HCO-1130a, HFO-1336, HCFC-244db, HFC-245fa, HFC-245cb, HFC- Also provided are compositions comprising at least one further compound selected from the group consisting of HCFC-1131, HCFO-1242zf, HCFO-1223xd, HCFC-233ab, HCFC-226ba, and HFC-227ca. The composition may contain greater than about 0% by weight to about 99% by weight of HCFC-244bb.

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Brief Description of the Drawings Figure 1 is a schematic diagram showing the reaction to produce HFO-1234yf from 243 db.

HFO-1234yf has been proposed to be used in particular as a refrigerant, heat transfer fluid, aerosol propellant, foam expansion agent. Advantageously, HFO-1234yf is disclosed in V.C. Papadimitriou, et al. in Physical Chemistry Chemical Physics, 2007, volume 9, pages 1-13], the global warming index (GWP) is also known to be low. Thus, HFO-1234yf is a good candidate for GWP to replace higher saturated HFC refrigerants.

In one embodiment, the present invention provides a process for the preparation of HFO-1234yf, HFO-1234z, HFO-1243zf, HCFC-243db, HCFC-244db, HFC-245cb, HFC-245fa, HCFO-1233xf, HCFO- HCFC-234ab, HCFC-243fa, ethylene, HFC-23, CFC-13, HFC-143a, HFC-152a, HFC-236fa, HCO-1130, HCO-1130a, HFO-1336, HCFC- At least one additional compound selected from the group consisting of HFO-1131, HFO-1141, HCFO-1242zf, HCFO-1223xd, HCFC-233ab, HCFC-226ba, HFC-227ca.

In one embodiment, the total amount of the additional compound (s) in the composition comprising HFO-1234yf ranges from greater than 0 wt% to less than 1 wt%.

In some embodiments, impurities present in HCFC-243db, HCFO-1233xf, and HCFC-244bb will remain intact during the reaction to produce HFO-1234yf, which is included in the further compound.

In a further embodiment, the present invention relates to a process for the preparation of a composition comprising HCFC-243db and at least one of ethylene, HFC-23, CFC-13, HFC-143a, HFC-152a, HFO-1234yf, HFO-1243zf, HFC-236fa, HCO- HFO-1234ze, HFO-1336, HCFC-244bb, HCFC-244db, HFC-245fa, HFC-245cb, HCFC-133a, HCFC-254fb, HCFC-1131, HCFO-1233xf, At least one additional compound selected from the group consisting of -253fb, HCFO-1223xd, HCFC-233ab, HCFC-226ba, and HFC-227ca.

In one embodiment, the total amount of the additional compound (s) in the composition comprising HCFC-243db ranges from greater than 0 wt% to about 99 wt%. In another embodiment, the total amount of additional compounds ranges from about 1 wt% to about 80 wt%. In another embodiment, the total amount of the additional compound (s) ranges from about 1 wt% to about 50 wt%. In another embodiment, the total amount of the additional compound (s) ranges from about 1% to about 30% by weight. In another embodiment, the total amount of the additional compound (s) ranges from about 1% to about 10% by weight.

In some embodiments, certain precursor compounds for HCFC-243db contain impurities that are present in HCFC-243db. In another embodiment, additional compounds are formed by the reaction of such precursor impurities. In another embodiment, the reaction conditions under which HCFC-243db is produced also result in the formation of byproducts, which means that additional compounds can be generated via alternative reaction paths depending on the particular conditions under which HCFC-243db is produced.

In another embodiment, the present invention provides a process for the preparation of HCFO-1233xf, HCFO-1233zd, HCFO-1232xd, HCFO-1223xd, HCFC-253fb, HCFC-233ab, HFO-1234yf, HFO- , HFC-143a, HFC-152a, HFO-1243zf, HFC-236fa, HCO-1130, HCO-1130a, HFO-1336, HCFC-244bb, HCFC-244db, HFC-245fa, HFC-245cb, At least one further compound selected from the group consisting of -254fb, HCFC-1131, HCFO-1242zf, HCFO-1223xd, HCFC-233ab, HCFC-226ba, HFC-227ca.

In one embodiment, the total amount of the additional compound (s) in the composition comprising HCFO-1233xf ranges from greater than 0 weight percent to about 99 weight percent. In another embodiment, the total amount of additional compounds ranges from about 1 wt% to about 80 wt%. In another embodiment, the total amount of the additional compound (s) ranges from about 1 wt% to about 50 wt%. In another embodiment, the total amount of the additional compound (s) ranges from about 1% to about 30% by weight. In another embodiment, the total amount of the additional compound (s) ranges from about 1% to about 10% by weight.

In some embodiments, certain precursor compounds for HCFO-1233xf contain impurities that appear at HCFO-1233xf. In another embodiment, additional compounds are formed by the reaction of such precursor impurities. In another embodiment, the reaction conditions under which HCFO-1233xf is produced also result in the formation of by-products, which means that additional compounds can be generated in an alternative reaction path depending on the particular conditions under which HCFO-1233xf is produced.

In another embodiment, the present invention provides a process for the preparation of HCFC-244bb, HCFO-1233zd, HCFO-1232xd, HCFO-1223xd, HCFC-253fb, HCFC-233ab, HFO-1234yf, HFO-1234ze, , HFC-143a, HFC-152a, HFO-1243zf, HFC-236fa, HCO-1130, HCO-1130a, HFO-1336, HCFC-244db, HFC-245fa, HFC-245cb, At least one further compound selected from the group consisting of -254fb, HCFC-1131, HCFO-1242zf, HCFO-1223xd, HCFC-233ab, HCFC-226ba, HFC-227ca.

In one embodiment, the total amount of the additional compound (s) in the composition comprising HCFC-244bb ranges from greater than 0 wt% to about 99 wt%. In another embodiment, the total amount of additional compounds ranges from about 1 wt% to about 80 wt%. In another embodiment, the total amount of the additional compound (s) ranges from about 1 wt% to about 50 wt%. In another embodiment, the total amount of the additional compound (s) ranges from about 1% to about 30% by weight. In another embodiment, the total amount of the additional compound (s) ranges from about 1% to about 10% by weight.

In some embodiments, certain precursor compounds for HCFC-244bb contain impurities that are present in HCFC-244bb. In another embodiment, additional compounds are formed by the reaction of such precursor impurities. In another embodiment, the reaction conditions under which HCFC-244bb is produced also produce by-products which subsequently appear in the HCFC-243db composition, which may generate additional compounds with alternative reaction pathways depending on the particular conditions under which HCFC- .

The compositions disclosed herein, including HFO-1234yf, can be used in a wide range of applications including, but not limited to, low heat transfer compositions with low Global Warming Potential (GWP), aerosol propellants, foaming agents, foaming agents, solvents, detergents, carrier fluids, coordination desiccants, buffing abrasives, polymerization media, polyolefins and polyurethanes Gaseous dielectrics, fire extinguishers, and fire suppressants in liquid or gaseous form. The disclosed composition can act as a working fluid used to transfer heat from a heat source to a heat sink. Such a heat transfer composition may also be useful as a refrigerant in a cycle where the fluid undergoes a phase change, i. E., From liquid to gas and back again, or vice versa.

Examples of heat transfer systems include, but are not limited to, air conditioners, freezers, refrigerators, heat pumps, water chillers, flooded evaporator chillers, direct expansion chillers, But are not limited to, a walk-in cooler, a heat pump, a mobile refrigerator, a mobile air conditioning unit, and combinations thereof.

As used herein, a mobile refrigeration unit, mobile air conditioning or mobile heating unit refers to any refrigeration, air conditioner, or heating device included in a transportation unit for road, rail, sea or air. In addition, the mobile refrigeration or air conditioner unit is independent of any mobile carrier and includes a device known as a " intermodal " system. Such a composite system includes a "swap body" (combined with road / rail transport) as well as a "container" (sea / land transport combined).

As used herein, a stationary heat transfer system is a system associated with or attached to any of a variety of buildings. Such fixed applications may be stationary air conditioning and heat pumps (including but not limited to windows, ductless, ducted, packaged, including, but not limited to, chillers, high temperature heat pumps, residential, commercial or industrial air conditioning systems) including packaged terminals, coolers, and rooftop systems that are external but connect to the building. In stationary refrigeration applications, the disclosed compositions can be used in commercial, industrial or residential refrigerator and freezers, ice makers, self-contained coolers and refrigerators, bayonet evaporative coolers, direct inflatable coolers, walk-in and reach- And freezers, and combination systems. In some embodiments, the disclosed compositions can be used in a supermarket refrigerator system.

The compounds that make up the disclosed compositions are defined in Table 1.

[Table 1]

HCFC-243db, HCFO-1233xf, and HCFC-244bb are available from professional chemical manufacturers, including SynQuest Laboratories, Inc. (Alla Chia, FL) Or may be prepared as described herein.

For example, HCFC-243db, HCFO-1233xf, and HCFC-244bb are prepared by non-catalytic chlorination of HFO-1243zf, as described in International Patent Publication WO2008 / 054782, published May 8, . In addition, HCFO-1233xf and HCFC-244bb can be prepared by catalytic fluorination of 243 db as described in International Patent Publication WO2008 / 054781, published May 8, Additional compounds present in each of the disclosed compositions will depend on the method of preparation.

In some embodiments, certain precursor compounds for HCFC-243db, HCFO-1233xf, or HCFC-244bb contain impurities that appear as additional compounds in the compositions described hereinafter. In another embodiment, such a precursor compound may itself react during 243db formation to form additional compounds that later appear in the HCFC-243db composition. In another embodiment, reaction conditions in which HCFC-243db, HCFO-1233xf, or HCFC-244bb are produced also produce byproducts, which can cause unintended reaction paths to occur simultaneously with HCFC-243db, HCFO-1233xf, or HCFC-244bb , And the amount and identity of such additional compounds will depend on the particular conditions under which HCFC-243db, HCFO-1233xf or HCFC-244bb are produced.

In one embodiment, HFO-1234yf can be generated in a single step from HCFC-243db. In another embodiment, the reaction sequence may be performed stepwise. In another embodiment, HCFO-1233xf can be generated from HCFC-243db, and then HCFO-1233xf can be directly converted to HFO-1234yf. In another embodiment, HCFC-244bb can be generated from HCFC-243db, and then HCFC-244bb can be converted to HFO-1234yf.

The fluorochlorination of HFO-1243zf

In some embodiments, HFO-1243zf can be used to produce HCFC-243db, HCFO-1233xf, HCFC-244db, and / or HFO-1234yf by fluorochlorination. HFO-1243zf is this. children. Available from EI DuPont de Nemours and Company of Wilmington, Del., USA.

The fluorochlorination reaction may be carried out in a liquid phase or a vapor phase. In the case of the liquid phase embodiment of the present invention, the reaction of HFO-1243zf with HF and Cl ₂ is carried out in a liquid phase reactor operating in batch, semi-batch, semi-continuous, . In a batch mode, HFO-1243zf, Cl ₂ , and HF are combined in an autoclave or other suitable reaction vessel and heated to the desired temperature.

In one embodiment, this reaction is performed by supplying Cl ₂ to a liquid phase reactor containing HF and HFO-1243zf, or supplying HFO-1243zf and Cl ₂ to a liquid phase reactor containing HF, The reaction product formed by the initial heating is supplied in a mixture containing HF and Cl ₂ in a semi-batch manner. In another embodiment, HF and Cl ₂ may be fed to a liquid phase reactor containing a mixture of HFO-1243zf and the reaction product formed by the reaction of HF, Cl ₂ , and HFO-1243zf. In another embodiment of the liquid phase process, HF, Cl ₂ , and HFO-1243zf can be simultaneously fed in the desired stoichiometric ratio to a reactor containing a mixture of HF and the reaction product formed by the reaction of HF, Cl ₂ , and HFO-1243zf have.

Suitable temperatures for the reaction of HF and Cl ₂ with HFO-1243zf in the liquid phase reactor are from about 80 ° C to about 180 ° C in one embodiment and from about 100 ° C to about 150 ° C in another embodiment. Higher temperatures typically cause a greater conversion of HFO-1243zf.

A suitable molar ratio of the total amount of HF to HFO-1243zf fed to the liquid phase reactor is at least stoichiometric in one embodiment, and in another embodiment from about 5: 1 to about 100: 1. An embodiment wherein the molar ratio of HF to HFO-1243zf is from about 8: 1 to about 50: 1 is noted. A suitable molar ratio of the total amount of Cl ₂ to HFO-1243zf fed to the liquid phase reactor is from about 1: 1 to about 2: 1.

In a liquid phase process, the reactor pressure is not critical and in batch reactions is the system's native pressure, usually at reaction temperature. The pressure of the system increases as the hydrogen substituent in the starting material and the intermediate reaction product is replaced by chlorine, and as the chlorine substituent is replaced by fluorine to form hydrogen chloride. In a continuous process, further products of low boiling point of the reaction, for example, HCl, HFO-1234yf (CF 3 CF = CH 2), E / Z-1234ze (E / Z-CF 3 CH = CHF), and HFC- a _{245cb (CF 3 CF 2 CH 3} ), selectively passing through the condenser column or packing, it is possible to set the pressure of the reactor in such a way that the exhaust from the reactor. In this manner, higher boiling intermediates remain in the reactor and volatile products are removed. Typical reactor pressures are from about 209 psig to about 6,994 psig.

In some embodiments the reaction is carried out using a liquid phase process, the carbon, AlF, which can be used catalyst _3, BF _3, FeCl _3-a F _a (wherein, a is 0-3 Im), a support FeX on carbon ₃ , SbCl _3-a F _a , AsF ₃ , MCl _5-b F _b wherein b is 0-5 and M is Sb, Nb, Ta, or Mo, and M'Cl _{4 -c} F _c Wherein c is from 0 to 4 and M 'is Sn, Ti, Zr, or Hf. In another embodiment, the catalyst for the liquid phase process is MCl _5-b F _b wherein b is from 0 to 5 and M is Sb, Nb, or Ta.

In another embodiment, the reaction of HF and Cl ₂ with HFO-1243zf is carried out on a vapor. Typically, a heated reactor is used. A number of reactor arrangements are possible including the order of reaction of HFO-1243zf and HF and Cl ₂ , as well as the horizontal or vertical orientation of the reactor. In one embodiment of the present invention, HFO-1243zf can be initially vaporized and fed to the reactor as a gas.

In another embodiment of the present invention, HFO-1243zf can be contacted with HF in a pre-reactor, optionally in the presence of Cl ₂ , prior to reaction in the vapor phase reactor. In one embodiment, the pre-reactor can be empty. In another embodiment, the reactor comprises a suitable packing, such as nickel available from Monel < (R) > under the trade name Special Metals Corp. (New Hartford, (Hereinafter referred to as " Monel "), a nickel-based alloy commercially available under the trade name Hastelloy (registered trademark) from Haynes International of Kokomo, Or other materials that are inert to HCl and HF to enable efficient mixing of HFO-1243zf and HF vapors, as well as other nickel alloys such as " HASSTELLO ") or other nickel alloy turning or wool.

Suitable temperatures for the pre-reactor are from about 80 캜 to about 250 캜 in one embodiment, and from about 100 캜 to about 200 캜 in another embodiment. Temperatures above about 100 DEG C cause some conversion of HFO-1243zf to compounds with a higher degree of fluorination. The higher temperature causes a larger conversion of HFO-1243zf into the reactor and a greater degree of fluorination of the converted compound. Under such conditions, for example, the mixture of HF, Cl ₂ , and HFO-1243zf is converted to a mixture containing mainly HCFC-243db and HCFC-244db (CF ₃ CHClCH ₂ F).

The degree of fluorination reflects the number of fluorine substituents replacing chlorine substituents in HFO-1243zf and its chlorinated product. For example, HCFC-253fb has a higher degree of fluorination than HCC-250fb, and HFO-1243zf has a higher degree of fluorination than HCO-1240zf.

The molar ratio of the total amount of HF to HFO-1243zf in the pre-reactor is, in one embodiment, about 50: 1 to the approximate stoichiometric ratio of the total amount of HF to HFO-1243zf. In another embodiment, the molar ratio of the total amount of HF to HFO-1243zf in the pre-reactor is about 2: 1 to about 30: 1 of the stoichiometric ratio of the total amount of HF to HFO-1243zf. In another embodiment, the molar ratio of the total amount of HF to HFO-1243zf is present in the pre-reactor and no additional amount of HF is added to the vapor phase reaction zone.

In another embodiment, HFO-1243zf can be contacted with Cl ₂ in a pre-reactor prior to reaction in the vapor phase reactor, optionally in the presence of HF.

Suitable temperatures for the pre-reactor for this embodiment of the invention are from about 80 캜 to about 250 캜, preferably from about 100 캜 to about 200 캜. Under these conditions, at least a portion of HFO-1243zf is converted to HCFC-243db. Higher temperatures typically cause a higher degree of halogenation of HFO-1243zf.

The degree of halogenation reflects the total number of halogen substituents (chlorine + fluorine) in the halopropane and / or halopropene product. For example, the degree of halogenation (i.e., 4) of HFO-1234yf is greater than the degree of halogenation (i.e., 3) of HFO-1243zf.

The molar ratio of Cl ₂ to the total amount of HFO-1243zf is, in one embodiment, from about 0.5: 1 to about 2: 1. In another embodiment, the molar ratio of Cl ₂ to the total amount of HFO-1243zf is from about 1.1: 1 to about 1: 1.

In one embodiment, HFO-1243zf is optionally vaporized in the presence of HF and fed to the pre-reactor or to the vapor phase reactor with HF and Cl ₂ .

Suitable temperatures for the vapor phase reaction are from about 120 < 0 > C to about 500 < 0 > C. Temperatures of about 250 ° C to about 350 ° C are advantageous for the formation of HFO-1234yf and HFC-245cb. Temperatures of about 350 ° C to about 450 ° C are advantageous for the formation of HFO-1234ze, HFC-245fa, and HCFO-1233zd. At a temperature of about 250 ° C to about 450 ° C, some HCFO-1233xf are also produced. Higher temperatures cause greater conversion of HFO-1243zf and greater degrees of fluorination and halogenation in the converted compound.

Suitable reactor pressures for the vapor phase reactor may range from about 101 to about 3040 psig (1 to about 30 atmospheres). A pressure of from about 1520 to about 2533 kPa (15 to about 25 atmospheres) can advantageously be used to promote the separation of HCl from other reaction products, with suitable reaction times ranging from about 1 to about 120 seconds, preferably from about 5 To about 60 seconds.

The molar ratio of the total amount of HF to HFO-1243zf for the vapor phase reaction is, in one embodiment, about stoichiometric ratio of the total amount of HF to HFO-1243zf to about 50: 1, in another embodiment from about 10: It is about 30: 1.

In one embodiment, a catalyst is used in the reaction zone for the vapor phase reaction of HF and Cl ₂ with HFO-1243zf. Chlorofluorination catalysts that can be used for vapor phase reactions include carbon; black smoke; Alumina; Fluorided alumina; Aluminum fluoride; Alumina supported on carbon; Aluminum fluoride supported on carbon; Fluorinated alumina supported on carbon; Magnesium fluoride supported on aluminum fluoride; Metals (including elemental metals, metal oxides, metal halides, and / or other metal salts); A metal supported on aluminum fluoride; A metal supported on the fluorinated alumina; A metal supported on alumina; And a metal supported on carbon; Mixtures of metals are included.

Iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, manganese (which is supported on alumina, aluminum fluoride, fluorinated alumina, or carbon) , Rhenium, scandium, yttrium, lanthanum, titanium, zirconium, and hafnium, copper, silver, gold, zinc and / or metals of atomic number 58 to 71 (i.e., lanthanide metals). In one embodiment, when used on a support, the total metal content of the catalyst is from about 0.1 to about 20% by weight, based on the total weight of the catalyst; In other embodiments, it will be from about 0.1 to about 10 weight percent, based on the total weight of the catalyst.

Chloro fluoride catalyst suitable for the vapor phase reaction, the chromium (III) oxide (Cr ₂ O _3); Cr ₂ O _{3 in} which another metal such as a magnesium halide or zinc halide is supported on Cr ₂ O ₃ ; Chromium (III) halide supported on carbon; A mixture of chromium and magnesium (including elemental metals, metal oxides, metal halides, and / or other metal salts) selectively supported on the graphite; And mixtures of chromium and other metals (including elemental metals, metal oxides, metal halides, and / or other metal salts) selectively supported on graphite, alumina, or aluminum halides such as aluminum fluoride Chromium-containing catalyst.

Cr-containing catalysts are well known in the art. These are prepared by either precipitation or impregnation as described generally in Satterfield, pages 87-112 of Heterogeneous Catalysis in Industrial Practice, 2 ^nd edition (McGraw-Hill, New York, 1991) can do.

A crystalline alpha-chromium oxide in which about 0.05 atom% to about 6 atom% chromium atoms in the alpha-chromium oxide lattice have been replaced by a trivalent cobalt atom, and a crystalline alpha-chromium oxide in the alpha-chromium oxide lattice that has been treated with a fluorinating agent, A chlorofluorination catalyst comprising at least one chromium-containing component selected from the group consisting of crystalline alpha-chromium oxides in which atomic% of chromium atoms have been replaced by trivalent cobalt atoms. Such catalysts are disclosed in U.S. Patent Publication No. 2005/0228202, including its preparation.

Optionally, the metal-containing catalysts described above may be pretreated with HF. This pretreatment can be accomplished, for example, by placing the metal-containing catalyst in a suitable vessel and then passing HF across the metal-containing catalyst. In one embodiment, such a vessel may be the reactor used to carry out the chlorofluorination reaction. In one embodiment, the pretreatment time is from about 15 minutes to about 300 minutes and the pretreatment temperature is from about 200 ° C to about 450 ° C.

In one embodiment, the product mixture comprises HFC-245cb, HFC-245fa, HFO-1234yf, HFO-1234ze, HCFO-1233zd and HCFO-1233xf.

In one embodiment, halopropane by-products that may be formed in the chlorofluorination reaction with higher degrees of halogenation and / or fluorination than pentafluoropropane include CF ₃ CCl ₂ CF ₃ (CFC-216aa), CF ₃ CClFCClF _{2 (CFC-216ba), CF 3} CClFCF 3 (CFC-217ba), CF 3 CF 2 CClF 2 (CFC-217ca), CF 3 CHFCF 3 (HFC-227ea), CF 3 CF 2 CHF 2 (HFC-227ca), _{CF 3 CClFCHF 2 (HCFC-226ba} ), CF 3 CF 2 CHClF (HCFC-226ca), CF 3 CHClCF 3 (HCFC-226da), CF 3 CCl 2 CHF 2 (HCFC-225aa), CF 3 CClFCHClF (HCFC-225ba _{), CF 3 CF 2 CHCl 2} (HCFC-225ca), CF 3 CCl 2 CClF 2 (CFC-215aa), CF 3 CClFCCl 2 F (CFC-215bb), CF 3 CCl 2 CCl 2 F (HCFC-214ab), CF ₃ CCl ₂ CHClF (HCFC-224aa), and CF ₃ CClFCHCl ₂ (HCFC-224ba).

In one embodiment, the halopropene byproduct, which can be formed in a chlorofluorination reaction having a higher degree of halogenation than tetrafluoropropene, includes CF ₃ CCl═CHCl (HCFO-1223xd).

In one embodiment, the product is selected from the group consisting of HCFC-243db and ethylene, HFC-23, CFC-13, HFC-143a, HFC-152a, HFO-1234yf, HFO-1243zf, HFC-236fa, HCO- HFO-1234ze, HFO-1336, HCFC-244db, HFC-245fa, HFC-245cb, HCFC-133a, HCFC-254fb, HCFC-1131, HCFO-1233xf, HCFO-1233zd, HCFO- 1223xd, HCFC-233ab, HCFC-226ba, and HFC-227ca.

The product mixture produced by the process of the present invention can be used to produce (i) the product compounds HFC-245cb, HFC-245fa, HFO-1234yf, HFO-1234ze, HCFO-1233zd and HCFO-1233xf, _2, (iii) further contains a by-product, for example a high boiling _{point, CF 3 CHClCH 2 Cl (HCFC} -243db), CF 3 CHClCH 2 F (HCFC-244bb) and (iv) chlorinated by-products, e.g., C ₃ If the process comprises HCl ₃ F ₄ , C ₃ HCl ₂ F ₅ , C ₃ HClF _6, C ₃ Cl ₃ F ₅ , and C ₃ Cl ₂ F ₆ , a separation process such as distillation will recover the product compound Can be used.

Fluorination of HCFC-243db

In some embodiments, HCFC-243db can be used to produce HCFC-HCFO-1233xf, HCFC-244db, and / or HFO-1234yf by fluorination. This reaction is shown in Fig. The fluorination reaction may be carried out in a liquid phase or a vapor phase. For the liquid phase embodiments of the present invention, the reaction of HCFC-243db with HF may be performed in a liquid phase reactor operating in batch, semi-batch, semi-continuous or continuous mode. In the batch mode, the starting HCFC-243db and HF are combined in an autoclave or other suitable reaction vessel and heated to the desired temperature.

In one embodiment, this reaction can be carried out by supplying HF to a liquid phase reactor containing HCFC-243db, or by supplying HCFC-243db to a liquid phase reactor containing HF, or by reaction formed by initial heating of HCFC-243db and HF Is carried out in a semi-batch manner by supplying HF to the mixture containing the product and HF. In another embodiment, HF may be fed to a liquid phase reactor containing a mixture of HCFC-243db and the reaction product formed by the reaction of HF with HCFC-243db. In another embodiment of the liquid phase process, HF and HCFC-243db can be simultaneously fed in the desired stoichiometric ratio to a reactor containing a mixture of HF and the reaction product formed by the reaction of HF with HCFC-243db.

Suitable temperatures for the reaction of HF with HCFC-243db in the liquid phase reactor are, in one embodiment, from about 80 ° C to about 180 ° C, in another embodiment from about 100 ° C to about 150 ° C. Higher temperatures typically cause a greater conversion of HCFC-243db.

The suitable molar ratio of HF to HCFC-243db fed to the liquid phase reactor is at least stoichiometric in one embodiment, and in another embodiment from about 5: 1 to about 100: 1. HF to HCFC-243db molar ratio of about 8: 1 to about 50: 1.

In a liquid phase process, the reactor pressure is not critical and in batch reactions is the system's native pressure, usually at reaction temperature. The pressure of the system increases with the formation of hydrogen chloride by replacing the chlorine substituent by fluorine in HCFC-243db and intermediate reaction products. In a continuous process, further products of low boiling point of the reaction, for example, HCl, CF ₃ CF = CH _2, and is passed through the _{E / Z-CF 3 CH =} CHF, the selective a column or a condenser packed with, the reactor It is possible to set the pressure of the reactor in such a manner as to exhaust it. In this manner, higher boiling intermediates remain in the reactor and volatile products are removed. Typical reactor pressures are from about 209 psig to about 6,994 psig.

In an embodiment the reaction is carried out using a liquid phase process, the carbon, AlF, which can be used catalyst _3, BF _3, FeCl _3-a F _a (wherein, a is 0-3 Im) and ₃ the support FeX on carbon _{, SbCl 3-a F a,} AsF 3, MCl 5-b F b ( wherein, b is from 0 to 5 and M is Sb, Nb, Ta, or Mo Im), and M'Cl _4-c F _c (wherein , c is 0 to 4, and M 'is Sn, Ti, Zr, or Hf. In one embodiment, the catalyst for the liquid phase process is MCl _5-b F _b , where b is from 0 to 5 and M is Sb, Nb, or Ta.

In one embodiment, the reaction of HF with HCFC-243db is carried out on a vapor. Typically, a heated reactor is used. A number of reactor arrangements are possible, including the horizontal or vertical orientation of the reactor, as well as the order of reaction of the starting material and HF. In one embodiment, HCFC-243db can be initially vaporized and fed to the reactor as a gas.

In another embodiment of the present invention, HCFC-243db can be contacted with HF in the pre-reactor before reacting in the vapor phase reactor. The pre-reactor may be empty, but is preferably packed with a suitable packing, such as a nickel-copper alloy commercially available from Special Metals Corporation (New Hartford, NY) under the trade name Monel (TM), Hastelloy Or other nickel alloy turning or wool, or other materials inert to HCl and HF to enable efficient mixing of HCFC-243db and HF vapors.

Suitable temperatures for the pre-reactor are from about 80 캜 to about 250 캜 in one embodiment, and from about 100 캜 to about 200 캜 in another embodiment. Temperatures above about 100 [deg.] C cause some conversion of HCFC-243db to compounds with a higher degree of fluorination. Higher temperatures result in a larger conversion of HCFC-243db entering the reactor and a greater degree of fluorination of the converted compound. Under such conditions, for example, is a mixture of HF and HCFC-243db is converted mainly of a mixture containing HF, HCl, HCFC-243db, HCFC-244db (CF 3 CHClCH 2 F), and HCFO-1233xf.

The degree of fluorination reflects the number of fluorine substituents replacing chlorine substituents in HCFC-243db and its fluorinated products. For example, HFO-1234yf exhibits a higher degree of fluorination than HCFO-1233xf.

The molar ratio of the total amount of HF to HCFC-243db in the pre-reactor is, in one embodiment, about the stoichiometric ratio of the total amount of HF to HCFC-243db to about 50: 1. In another embodiment, the molar ratio of the total amount of HF to HCFC-243db in the pre-reactor is about 2: 1 to about 30: 1 of the stoichiometric ratio of the total amount of HF to HCFC-243db. In another embodiment, the molar ratio of the total amount of HF to HCFC-243db is present in the pre-reactor and no additional amount of HF is added to the vapor phase reaction zone.

In one embodiment, HCFC-243db and HF are vaporized and fed to the pre-reactor or to the vapor phase reactor.

Suitable temperatures for the vapor phase reaction are from about 120 < 0 > C to about 500 < 0 > C. Temperatures in the range of from about 300 ° C to about 350 ° C are advantageous for the formation of HFO-1234yf and HFC-245cb and HCFO-1233xf. Temperatures in the range of about 350 ° C to about 450 ° C are advantageous for further formation of HFO-1234ze, HFC-245fa, and HCFO-1233zd. The higher temperature causes a larger conversion of HCFC-243db and a greater degree of fluorination in the converted product. Reactor temperatures of about 150 ° C to about 275 ° C are advantageous for the formation of HCFO-1233xf as the main product.

Suitable reactor pressures for the vapor phase reactor may range from about 1 to about 30 atmospheres. A pressure of about 15 to about 25 atmospheres may be advantageously used to promote the separation of HCl from other reaction products, and suitable reaction times may vary from about 1 to about 120 seconds, preferably from about 5 to about 60 seconds have.

The amount of HF to HCFC-243db for the vapor phase reaction is in the approximate stoichiometric ratio of the amount of HF to HCFC-243db in one embodiment to about 50: 1 in another embodiment, in another embodiment about 10: It is about 30: 1.

In some embodiments, a catalyst is used in the reaction zone for the vapor phase reaction of HF and HCFC-243db. Fluorination catalysts that can be used for vapor phase reactions include carbon; black smoke; Alumina; Fluorinated alumina; Aluminum fluoride; Alumina supported on carbon; Aluminum fluoride supported on carbon; Fluorinated alumina supported on carbon; Magnesium fluoride supported on aluminum fluoride; Metals (including elemental metals, metal oxides, metal halides, and / or other metal salts); A metal supported on aluminum fluoride; A metal supported on the fluorinated alumina; A metal supported on alumina; And a metal supported on carbon; Mixtures of metals are included.

Iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, manganese (which is supported on alumina, aluminum fluoride, fluorinated alumina, or carbon) , Rhenium, scandium, yttrium, lanthanum, titanium, zirconium, and hafnium, copper, silver, gold, zinc and / or metals of atomic number 58 to 71 (i.e., lanthanide metals). In some embodiments, when used on a support, the total metal content of the catalyst is from about 0.1 to about 20 weight percent, based on the total weight of the catalyst; In other embodiments, it will be from about 0.1 to about 10 weight percent, based on the total weight of the catalyst.

In typical fluorination catalyst for the vapor phase reaction of the present invention chromium (III) oxide (Cr ₂ O _3); Cr ₂ O _{3 in} which another metal such as a magnesium halide or zinc halide is supported on Cr ₂ O ₃ ; Chromium (III) halide supported on carbon; A mixture of chromium and magnesium (including elemental metals, metal oxides, metal halides, and / or other metal salts) selectively supported on the graphite; And mixtures of chromium and other metals (including elemental metals, metal oxides, metal halides, and / or other metal salts) selectively supported on graphite, alumina, or aluminum halides such as aluminum fluoride Chromium-containing catalyst.

Cr-containing catalysts are well known in the art. These are prepared by either precipitation or impregnation as described generally in Satterfield, pages 87-112 of Heterogeneous Catalysis in Industrial Practice, 2 ^nd edition (McGraw-Hill, New York, 1991) can do.

A crystalline alpha-chromium oxide in which about 0.05 atom% to about 6 atom% chromium atoms in the alpha-chromium oxide lattice have been replaced by a trivalent cobalt atom, and a crystalline alpha-chromium oxide in the alpha-chromium oxide lattice that has been treated with a fluorinating agent, At least one chromium-containing component selected from the group consisting of crystalline alpha-chromium oxides in which the atomic percent chromium atoms have been replaced by trivalent cobalt atoms. Such catalysts are disclosed in U.S. Patent Publication No. 2005/0228202, including its preparation.

Optionally, the metal-containing catalysts described above may be pretreated with HF. This pretreatment can be accomplished, for example, by placing the metal-containing catalyst in a suitable vessel and then passing HF across the metal-containing catalyst. In one embodiment of the invention, such a vessel may be a reactor used to carry out the fluorination reaction of the present invention. Typically, the pretreatment time is from about 15 minutes to about 300 minutes and the pretreatment temperature is from about 200 ° C to about 450 ° C.

In one embodiment of the present invention, the product mixture comprises HFC-245cb, HFC-245fa, HFO-1234yf, HFO-1234ze, HCFO-1233zd and HCFO-1233xf.

Fluorination of HCFO-1233xf

In some embodiments, HCFO-1233xf may be used to prepare HCFC-HCFC-244bb, and / or HFO-1234yf. This reaction is shown in Fig.

In one embodiment, the reaction of HCFO-1233xf with HCFC-244bb can be carried out in a liquid phase. In another embodiment, the reaction may be carried out on a vapor.

In one embodiment, the reaction of HCFO-1233xf with HCFC-244bb can be performed in a batch mode. In another embodiment, the reaction can be carried out in a continuous mode.

In one embodiment, the liquid phase reaction of HCFO-1233xf with HCFC-244bb can be carried out in the presence of a catalyst. In one embodiment, the catalyst may be a Lewis acid catalyst. In one embodiment, the catalyst may be a metal-halide catalyst. In another embodiment, the catalyst may be at least one catalyst selected from the group consisting of antimony halides, tin halides, thallium halides, iron halides, and combinations of two or more thereof. In another embodiment, the catalyst is antimony pentachloride (SbCl _5), antimony trichloride (SbCl _3), antimony pentafluoride (SbF _5), tin tetrachloride (SnCl _4), titanium tetrachloride (TiCl _4), an iron-trimethyl Chloride (FeCl ₃ ), and combinations thereof. In some embodiments, the reaction may be carried out using any known fluorination catalyst for liquid phase reaction.

In one embodiment, the reaction of HCFO-1233xf with HCFC-244bb can be carried out in the absence of a catalyst.

In one embodiment, the vapor phase reaction of HCFO-1233xf to HCFC-244bb can be carried out in the presence of a catalyst. In one embodiment, the reaction is carried out in the presence of a chromium-based catalyst, an iron-based catalyst, or a combination thereof. In one embodiment, the chromium-based catalyst is chromium oxide (e.g., Cr ₂ O ₃ ). In one embodiment, the iron-based catalyst may be FeCl ₃ on carbon.

In one embodiment, the vapor phase reaction of HCFO-1233xf to HCFC-244bb is carried out in the absence of a catalyst.

Dehydrochlorination of HCFC-244bb

In some embodiments, dehydrochlorination of HCFC-244bb is used to produce HFO-1234yf.

In one embodiment, the dehydrochlorination of HCFC-244bb to HFO-1234yf is carried out in the vapor phase.

In one embodiment, the vaporous dehydrochlorination is carried out in the presence of a catalyst. In one embodiment, the catalyst is selected from carbon and / or metal based catalysts. In one embodiment, the catalyst may be selected from activated carbon, a nickel-based catalyst, a palladium-based catalyst, or any combination of these catalysts. In one embodiment, the catalyst may be selected from the group consisting of Ni-mesh, palladium on carbon, palladium on aluminum oxide, or combinations thereof.

In one embodiment, HFO-1234yf is prepared by thermal dehydrochlorination of HCFC-244bb. In one embodiment, this reaction takes place in the absence of a catalyst. In one embodiment, HCFC-244bb is introduced into the reaction vessel where the temperature is maintained at a temperature sufficiently high to cause thermal dehydrochlorination of HCFC-244bb. In one embodiment, the temperature is high enough to cause thermal dehydrochlorination of HCFC-244bb at a percent conversion of at least 50%. In another embodiment, the temperature is high enough to cause thermal dehydrochlorination of HCFC-244bb with a percent conversion of at least 65%. In yet another embodiment, the temperature is high enough to cause thermal dehydrochlorination of HCFC-244bb at a percent conversion of at least 80%. In yet another embodiment, the temperature is high enough to cause thermal dehydrochlorination of HCFC-244bb at a percent conversion of at least 70% during at least 12 hours of continuous operation.

In one embodiment, HCFC-244bb is introduced into a reaction vessel where the temperature is maintained at a temperature ranging from about 500 ° C to about 700 ° C. In another embodiment, the temperature of the reaction vessel is maintained in the range of about 500 ° C to about 650 ° C. In yet another embodiment, the temperature of the reaction vessel is maintained at a temperature sufficiently high to cause pyrolysis of HCFC-244bb to HFO-1234yf with a selectivity of at least 80%. In another embodiment, the temperature of the reaction vessel is maintained at a temperature sufficiently high to cause pyrolysis of HCFC-244bb to HFO-1234yf with a selectivity of 85% or greater.

In one embodiment, the reaction zone is a reaction vessel comprised of a corrosion resistant material. In one embodiment, the material is selected from the group consisting of an alloy, for example, a nickel-based alloy such as Hastelloy®, a nickel-chrome alloy commercially available from Special Metals Corporation under the tradename Inconel® Nickel alloy or a fluoropolymer lining that is commercially available under the trade designation " Inconel (R) ") or Special Metals (New Hartford, NY).

In one embodiment, HCFC-244bb is preheated to a temperature of about 30 [deg.] C to about 100 [deg.] C at the vaporizer. In another embodiment, the HCFC-244bb is preheated to a temperature of about 30 [deg.] C to about 80 [deg.] C at the vaporizer.

In some embodiments, an inert diluent gas is used as the carrier gas for HCFC-244bb. In one embodiment, the selected carrier gas is nitrogen, argon, helium, or carbon dioxide.

Without further elaboration, it is believed that one skilled in the art using the teachings herein will be able to utilize the present invention to its fullest extent. The following specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any manner whatsoever.

Example

General procedure for product analysis

The following general procedure illustrates the method used to analyze the product of the fluorination reaction. A portion of the total reactor effluent was sampled on-line for organic product analysis using gas chromatography (GC / MS) with a mass selective detector. The gas chromatography was performed on an inert carbon support using a perfluoro (perfluoroborate) catalyst commercially available under the tradename Krytox (R) from E. I. Du Pont de Nemours & Co. (Wilmington, Del. A 6.1 m (20 ft.) Length x 0.32 cm (1/8 inch) diameter tube containing polyether was used. Helium flow was 30 ㎖ / min was (5.0 x 10- ⁷ ㎥ / sec). The gas chromatographic conditions were 60 ° C for an initial hold period of 3 minutes, followed by temperature programming at 6 ° C / minute to 200 ° C.

Preparation of 98% chromium / 2% cobalt catalyst

A solution of 784.30 grams of Cr (NO ₃ ) ₃ [9 (H ₂ O)] (1.96 moles) and 11.64 grams of Co (NO ₃ ) ₂ [6 (H ₂ O)] (0.040 moles) in 2000 ml of deionized water Solution. The solution was treated with 950 mL of 7.4 M aqueous ammonia solution until the pH reached about 8.5. The slurry was stirred overnight at room temperature and then evaporated to dryness at 110-120 ° C in air. The dried catalyst was then calcined in air at 400 < 0 > C for 24 hours before use.

Legend

243 db is CF ₃ CHClCH ₂ Cl. 244 db is CF ₃ CHClCH ₂ F.

245cb is CF ₃ CF ₂ CH _3. 245fa is CF ₃ CH ₂ CHF _2.

1234yf is CF ₃ CF = CH _2. 1233xf is CF ₃ CCl = CH _2.

1243zf is CH ₂ = CHCF ₃ . 233ab is CF ₃ CCl ₂ CH ₂ Cl.

1233zd is E- and / or Z-CHCl = CHCF _3. 226ba is CF ₃ CClFCHF ₂ .

1234ze is E- and / or Z-CHF = CHCF _3. 227ca is CF ₃ CF ₂ CHF _2.

1223 x d is E- and / or Z-CF ₃ CCl = CHCl. 244bb is CF ₃ CFClCH _3.

1141 is CHF = CH ₂ .

Examples 1 to 6

Chlorofluorination of HFO-1243zf

(21.4 grams, 15 ml, -12 to +20 mesh, (1.68 to 0.84 mm)) prepared above was placed in a 5 / Was placed in an 8 "(1.58 cm) diameter Inconel (TM) nickel metal reactor reactor tube (Special Metals, New Hartford, NY). The catalyst was pre-fluorinated by treatment with HF as follows. Was heated in a flow of nitrogen (50 cc / min) over a period of about 1.5 hours to 45-175 ° C. HF was then allowed to enter the reactor at a flow rate of 50 cc / min at a temperature of 175 ° C. for 1.3 hours. The reactor nitrogen flow was reduced to 20 cc / min and the HF flow was increased to 80 cc / min, and this flow was maintained for 0.3 h. The reactor temperature was then gradually increased over one hour to 400 ° C. During this period Later, HF and nitrogen flow was stopped, and the reactor desired The HFO vapor, HFO-1243zf, and Cl ₂ were then started to flow through the reactor. A portion of the reactor effluent was analyzed by on-line GC / MS.

The results of the various operating temperatures and HF, HFO-1243zf and chloro with fluoro in the 98/2 Cr / Co catalyst at the indicated molar ratio of HFO-1243zf Cl ₂ screen and shown in Table 2; Analytical data are provided in units of% GC area. The nominal catalyst bed volume was 15 cc; The contact time (CT) was 15 seconds. Example 1 and Example 2 were carried out in the absence of a catalyst.

[Table 2]

Examples 7 to 11

Fluorination of HCFC-243db

(21.4 grams, 15 mL, -12 to +20 mesh, 1.68 to 0.84 mm) of the 98% chromium / 2% cobalt catalyst prepared above was placed in a 5/8 " The catalyst was pre-fluorinated by treatment with HF as follows: The catalyst was heated to about 45 ° C to 175 ° C in a flow of nitrogen (50 cc / min) over about 1.5 hours. The HF was then allowed to enter the reactor at a flow rate of 50 cc / min for 1.3 hours at a temperature of 175 DEG C. The reactor nitrogen flow was reduced to 20 cc / min and the HF flow was increased to 80 cc / min The reactor temperature was then gradually increased over 1 hour to 400 DEG C. After this period the HF and nitrogen flow was stopped and the reactor was brought to the desired operating temperature. The reactor was then passed through HF vapor and HCFC-243db (CF ₃ CHClCH ₂ Cl). Part of the reactor effluent was analyzed by on-line GC / MS.

The results of the fluorination of HFC-243db with 98/2 Cr / Co catalyst at various operating temperatures and indicated molar ratios of HF and HCFC-243db are shown in Table 3; Analytical data are provided in units of% GC area. The nominal catalyst bed volume was 15 cc; The contact time (CT) was 15 seconds. Example 7 was carried out in the absence of a catalyst.

[Table 3]

Example 12

TaF ₅ Reaction of HFC-243db with HF in the presence of

210 mL of Hastelloy C tube was charged with 10.0 grams (0.0599 moles) of HCFC-243db and 25.4 grams (0.040 moles) of tantalum pentafluoride. The tube was then filled with 40.0 grams (2.0 moles) of hydrogen fluoride. The tube was heated to 150 DEG C and held at 149 DEG C to 150 DEG C for 8 hours with shaking. The tube was then cooled to room temperature and treated with 100 mL of water. The contents of the tube were drained and a small amount of organic layer was collected and neutralized. The sample had an untransformed HCFC-243 db of 91.1%; GC-MS analysis of the transformed product was as follows:

[Table 4]

Example 13

Fluorination of HCFO-1233xf to HCFC-244bb

Viscosity SbF ₅ 400 ㎖ a Hastelloy (trademark), dried and the contents of a small PTFE vial containing of 20 grams was poured into a shaker tube. The tube was closed and pressurized with nitrogen for leak test. Then, the shaker tube was cooled to less than -40 캜 using dry ice, evacuated slowly, and vacuumed. 75 grams (3.75 moles) of anhydrous HF, then 165 grams (1.26 moles) of HCFO-1233xf were condensed into the shaker tube. The shaker tube was placed in the barricade and shaking started.

The shaker tube was agitated at ambient temperature (about 20 to 23 ° C) and the pressure was between 145 and 172 psig (21 to 25 psig). After 2 hours, the shaking was stopped and 150 ml of water was carefully pumped into the shaker tube. The tube was allowed to stand overnight, then cooled to 0-5 < 0 > C in an ice bath, reduced in pressure, and the contents transferred to a plastic container. The container was placed on ice.

The contents of the vessel were poured into a polypropylene fractionation funnel containing some ice. The lower organic layer was bright amber in appearance. The organic layer was separated and chromatographed on silica gel using a mixture of approximately 50 mL of 4-mol (pH 7) phosphate buffer and 5 g of Pyrex (registered trademark) from Corning containing ice (approximately 100 mL) ) &Quot;). ≪ / RTI > The organic layer was again separated and poured into a dried Pyrex (TM) media bottle containing a small amount of anhydrous magnesium sulfate. The crude yield was 164.3 grams (about 120 mL, 86%).

GC / MS of the crude material indicated that this was mainly HCFC-244bb. Other components included 0.13% 245cb, 0.09% 245eb, 0.16% 1233xf, and a total of 12.2% by-products.

Example 14

Fluorination of HCFO-1233xf to HCFC-244bb

Viscosity SbF ₅ 400 ㎖ a Hastelloy (trademark), dried and the contents of a small PTFE vial containing of 20 grams was poured into a shaker tube. The tube was closed and pressurized with nitrogen for leak test. Then, the shaker tube was cooled to less than -40 캜 using dry ice, evacuated slowly, and vacuumed. 53 grams (2.65 moles) of anhydrous HF was transferred into the shaker tube and 227 grams (1.74 moles) of HCFO-1233xf were condensed into the cooled shaker tube. The shaker tube was placed in the barricade and shaking started.

The shaker tube was agitated at ambient temperature (about 18-21 ° C) and the pressure was between 110 and 138 psig (16-20 psig). After 2 hours, the shaking was stopped and 100 ml of water was carefully pumped into the shaker tube. The tube was allowed to stand overnight, cooled to 0-5 < 0 > C in an ice bath, vented, and the contents transferred to a plastic container. The container was placed on ice.

The contents of the vessel were poured into a polypropylene fractionation funnel containing some ice. The lower organic layer was bright amber in appearance. The organic layer was separated and placed in a Pyrex (R) media bottle containing approximately 50 mL of 4 molar (pH 7) phosphate buffer and ice (approximately 100 mL). The organic layer was again separated and poured into a dried Pyrex (TM) media bottle containing a small amount of anhydrous magnesium sulfate. The crude yield was 238.8 grams (about 170 mL, 91%).

GC / MS of the crude material indicated that this was mainly HCFC-244bb. Other components included 0.11% HFC-245cb, 0.10% HFC-245eb, 0.26% HCFO-1233xf, and a total of 9.7% by-products.

Example 15

Example 15 shows the conversion of HCFC-244bb (2-chloro-1,1,1,2-tetrafluoropropane) to HFO-1234yf (2,3,3,3-tetrafluoropropene) .

An empty Inconel (TM) tube (1.27 cm (1/2 inch) OD) with a heating area of about 30.5 cm (12 inches) was heated to a temperature of 500 ° C to 626 ° C and HFC-244bb was heated to 4.0 x 10 through a vaporizer set to 40 ℃ using a N ₂ sweep (sweep) of ^-8 ㎥ (2.4 sccm) it was fed to the 0.52 ㎖ / hour. The reactor effluent was analyzed using on-line GCMS and the results reported in mol%.

[Table 5]

Example 16

Example 16 illustrates the conversion of HCFC-244bb (2-chloro-1,1,1,2-tetrafluoropropane) to HFO-1234yf (2,3,3,3-tetrafluoropropane) .

An empty Inconel (registered trademark) tube (1.27 cm (1/2 inch) OD) with a heating area of about 30.5 cm (12 inches) was heated to 575 ° C and HFC-244bb was heated to 6.0 x ^10-8 m 3 0.0 > sccm) < / RTI > using a N ₂ sweep. The reactor was operated continuously for a total of 19 hours and samples were periodically taken and analyzed to determine the percent conversion of HFC-244bb and the selectivity to HFO-1234yf. The reactor effluent was analyzed using on-line GCMS, and the data in Table 6 below is the average of at least two on-line injections at certain conditions; The percentages are in mole%.

[Table 6]

Example 17

Example 17 demonstrates the dehydrochlorination of HCFC-244bb (2-chloro-1,1,1,2-tetrafluoropropane) in the presence of an activated carbon catalyst.

An Inconel (R) tube (1.27 cm (1/2 inch) OD) was filled with 4 cc (1.99 gm) pickled PCB Polyniian coconut shell carbon (6-10 mesh) from Calgon . HFC-244bb was supplied at 1.04 ml / hr through a carburettor set at 40 ° C using a N ₂ sweep of 4.0 x 10 ^-8 m 3 (2.4 sccm) while controlling the reactor temperature to 400 ° C, resulting in a total contact time of about 32 seconds Respectively.

The data in Table 7 shows the reactor effluent composition for this process to produce HFC-1234yf through HCl removal over an operating period of 7 hours using an activated carbon catalyst in mole%.

[Table 7]

Claims (10)

A refrigerant comprising HFO-1234yf, HFC-245cb, HCFO-1233xf and HFC-254eb wherein the amount of HFO-1234yf accounts for more than 99 weight percent of the refrigerant. The method of claim 1, further comprising the steps of: providing an air conditioner, a freezer, a refrigerator, a heat pump, a water chiller, a flooded evaporator chiller, a direct expansion chiller, A refrigerant used as a refrigerant in a centrifugal chiller, a walk-in cooler, a mobile refrigerator, a mobile air conditioning unit, or a combination thereof. The refrigerant as claimed in claim 1, wherein the refrigerant is used as a refrigerant in a cycle including a phase transition from liquid to gas and back again. The refrigerant according to claim 1, further comprising HFC-23. The refrigerant according to claim 4, further comprising HCFO-1223xd. The refrigerant of claim 1 comprising at least one of HFO-1234ze, HCFO-1233zd, HCFC-1131 and HFO-1141. 7. The refrigerant of claim 6 comprising HFO-1234ze. delete delete delete

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